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Ligand Engineering in Lanthanide-Titanium-Oxo Clusters: Preventing Charge Transfer to TiIV for High-Efficiency
Wei-Dong Liu1, Si-Wei Ying1, Zi-Jing She1
1State Key Laboratory of Physical Chemistry of Solid Surfaces, and Department of Chemistry, College of Chemistry and Chemical Engineering, Xiamen University, Xiamen, 361005, China.
None:
Lanthanide-titanium-oxo clusters (LTOCs) exhibit promising luminescence potential owing to their unique core structures. In this study, the impact of ligand-to-metal charge transfer (LMCT, M = TiIV) is systematically elucidated on the luminescence of LTOCs through crystal structure analysis, theoretical calculations, and photophysical measurements. The results reveal that the existence of the LMCT state disrupts the normal energy transfer process, thereby causing the failure of photo-excitation in LTOCs. By strategically replacing LMCT-inducing ligands with non-LMCT counterparts in Eu2Ti4 and Eu2Ti6 clusters, the remarkable enhancement is achieved in luminescence intensity. This study provides valuable insights into the rational design of high-performance luminescent LTOCs, highlighting ligand coordination environments as a critical design factor in LTOCs.
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